New azo dye



Patented Nov. 24, 1931 g I STATES RICHARD STI'TSSER,'OE-COLOGNE-DEUTZ, GERMANYQASSIGNOR 'roeENER I. AnrLInE WORKS, INO'J, .OF NEW YORK, N. Y., A GOR?OBATION'OEDEILAWARE' NEW Azo DYE No Drawing. Application filed anuary 25, 1928, Serial No. 249,496, and'i n Germany J'anuar371927.

The present invention relates to new azo dyestuffs and to a process of making the same, more particularly it relates to azo dyestufls of the probable general formula wherein R R and'R; represent benzene nuclei, R 'and one of R and R being substi-' 1 any substituent, e: g. alkylyhalogen, alkoxy,

excepted a sulfonic acid group. The new dyestufis'are obtainable by couplinga diazotized aminophenyl ben'zothiazole-monos ulfonic acid with a sulfonic acid ofan acetoacet anilide, or by ssulfonating a monoazo dyestuii' obtained from a diazotized mono-sulfonated or unsulfonated aminophenylrbenzothiazole and an, acetoacetanilide. For the purpose of my invention the two methods of preparing the new dyestuffs are equivalents. In accordance with the present invention, cotton dyestuffs of good fastness to water andlight and a great aflinityto' the fibre are produced. These dyestuffs can also be employed as pigment dyestuffs. In the form of their-alkali-metal salts they are,' when dried and pulverized generally yellow to orange powdersysoluble in water with a yellow 7 coloration, in 'sulfuric acid with a yellow to orange coloration. They yield, upon reduction with stannous chloride and hydrochloric acid; an aminophenyl-benzothiazole monosultonic acid, c-arnino-ac-etoacetic acid and an aminobenzene-mono-sulfonic acid. 40 The following examples will illustrate my invention:

Example 1.342 parts by weight of the sodium salt of dehydrothio-toluidine-orthomono-sulfonic acid (prepared according to the baking process from dehydrothio-toluidine sulfate by heating the same) are diazotized in the known manner with 69 parts by weight of sodium nitrite and 300 parts by weight of hydrochloric acid of 195 Be. The diazo compound which separates is filtered,

and their introduced at Cheater 287 parts by weight ofaeetoacetortho anisidide sulfonic' acid and 250 parts byr weight jofsodrum carbonate at about 10 C.*-NVhen the coupling is completed,the solution is heatedv to 6O? C. and saltedout,{whereupon"the-dye stufi' having in its free state the following formula: v

is filtered and ;dried.- It-forms a yellow powder, whichdyescotton greenish yellow shades. The dyeing produced is very fastto light and waterl The dyestuff also dyes viscose with the production of bright greenish yellow shadea This dyeingis" likewise fast to waters. The dyestufiicanlalsobe precipi+ tated in the form of a pigment dye following the'customary methods." Q i w Example 2.564,4 parts byfweight of the dyestufl' obtained fromr dehydrothio-toluidine-monosulfonic acid and acetoacet-orthochloranilide are dissolved in-5000 parts by 7 weight of sulfuric: acid monohydrate "while cooled in ice, 500 parts 'byweight of oleum containing of anhydride are then added, .and the sulfonating-mixture"isheated to 45 to 50;Guuntil the dyes'tulf hasbecome easily soluble. On completion of the sulfonation,

the whole isallowed toicooh'poured on to ice, and the precipitated dyestufi of the formula;

filtered'ofi'; it is then Washed free from sulfuric acid with water and redissolved in hot "water with sodium carbonate, filtered and "fonatin'g the azodyestuff obtainableby cool-' other known processes.

l6 stnffswhich process comprises couplinga di- 7 i salted out from its solution. The, dyestufl forms a yellow powder, which dyes cottonv yellow shades of satisfactory fastness prop.-

The same dyestufl'. can be obtained by suling- "dia'zotized dehydro-thio-toluidine with aceto acetorthoechloranilide.

Thesulfonation can also be carried l 1." Process for the manufacture of I azo dyeazotized aminophenyl-benzothiazole-monosulfonic acid with a mono-sulfonic acidof an acetoacetanilide. 2. Process-forthe manufacture of azo dyestuffswhich process comprises coupling diazotiz ed I dehydrothiotoluidine-ortho-monosulfonicacid with a mono-sulfonic acid of an" acetoacetanilidQ j 7 I 3. Process forthe manufacture of an azo dyestulf which process comprises coupling diazotized dehy'drothi'otoluidine-ortho-mono-V v sulfonic acid with acetoacet-ortho-anisidide,

sulfonic acid;

4:. As new -products,'the nionoazo dyestuffs of the probable general formula:

i on;

, I 0' i V V R1, C--R:N=N4-CH r .liIH-Ra I R and R represent benzene nnclei'; of which R 7 and one of R and R are substituted by a sulfonic-acid group and all I f of which may be further substituted substituents of the group consistin of alkyl, alkoxy and halogen, said dyestu s being in the'form oftheir alkali metal salts, when dried and pulverized, generally yellow to 7 orange powders, soluble in water with a yellowzcoloration, in sulfuric acid with a yellow to orange coloratiom; dyeing cotton yellow to orange shades of good fastness to light. and-water, being: suitable for the employment as pigment 'cdye'stufis and yielding, "upon i reduction with stannous chloride and hydrochloric acid, an aminophenyl-b enzo-thiazole-v mon'osulfonic acid, -amino-aceto-acetic acid iandf'an' amrnobenzene-mono-sulfon1c acid.

7 5. As a new product, the monoazo dyestufl' 7 having init'sfreestate-probably the formula:

SOzH

entry] ,7.'Asanew being in the form of its alkali metal salt, when dried and pulverized, a yellow powder, soluble in water and sulfuric acid with a yellow coloration, dyeing cotton greenish yellow '7 I shades and yielding, upon reduction with stannous chloride and hydrochloric acid dehydrothio toluidine 4 ortho mono sulfonic acid, wamino-aceto-acetic acid and l-amino- 2:methoXy-benzene l-sulfonic acid. 7

6.7 As new products, themonoaz'o' dyestuffs of thegeneral formula I V group, said dyestuffs being inthe form of their alkali metalsalts, when dried and pulverized, yellow powders, soluble in water and sulfuric acidwith' a yellow coloration, dyeing cotton yellow shades, and yielding, upon reduction with st-annous chloride andhydrochloric acid, dehydro-thio-toluidine-ortho- 1 monosulfonic acid, a-amino-acetoacetic acid and an amino-sulfomc acid of the benzene 1 series. I I I a product, the monoazo dyestufl' having in its free statethe following probable formula: I l I V j being in :the form of its 'yalkali metal salt, when dried andpulverized, a yellow-powder,

soluble in water and sulfuric. acid with a yel- I in wherein R stands for a residue of the benzene series which is substituted by a sulfonic acid 

